Method of treating marine-animal oils.



No. 823,361. PATENTED JUNE 12, 1906. M. POTOLOWSKY. METHOD OF TREATINGMARINE ANIMAL OILS.

APPLICATION FILED JAN. 27. 1902.

UNITED STATES PATENT oFFIon;

MICHAEL POTOLO\-VSKY, OF MOSCOW, RUSSIA.

METHOD OF TREATING MARINE-ANIMAL OILS.

To It/l II'lI-H'HI: it In. 1 concern:

Be it known that I, M IGHAEL Io'roLowsKY, asub ect of the Emperor ofRussia, residing at Moscow, Russia, have invented a certainv new anduseful .\lethod of Treating Marinedo hereby declare the f 01- 1 AnimalOils; and 1 lowing to be tion of the others skilled in the art to whichit appertains to make and use the same.

My invention relates to a new method of treating marine animal oils. It.is well known that such marine-animal oils consist principally oflycerids of the liquid fatty acids (up to eig ityfive per cent.) andowing to the insignificant proportion of the glycerids 01 the solidfatty acids contained in such marine-animal oils have been employedalmost exclusively for the manufacture of soft soap only, not beincapable of use for ordinary hard soap and, candles owing to their strongdisagreeable smell, which it has been impossible hitherto to remove.

It is the object of my invention to remove this disagreeable odor frommarine-animal oils and at the same time to'produce a new product whichowing to its resemblance to tallow may Well be designated. as marineanimal-oil tallow.

In carrying out my process and in obtaining my new product I preferablyproceed in the manner hereinafter pointed out in connection with theaccompanying drawings, which show an apparatus suitable for theperformance of my process.

In the drawings,-Figure 1 is a vertical section of the apparatus; and,Fig. 2 a plan view of the same, partly in section.

Referring to the drawings, a is a tanker reservoir located within acasing a, a space i being left between the two, as shown in Fig. 1. Thetank a is provided with a lid 6, having a manhole covered by amanhole-plate 0. Through the manhole the marine-animal oil to be treatedmay be poured, into the tank. An acid-supply pipe (2 enters the tankthrough its cover, being provided inside with a series of small holes.Through this pipe sulfuric acid may be sprayed into the marine-animaloil. Blades e are provided within the tank for the purpose of stirringthe mixture, which blades are rotated by means of avertical shaft f,having arms f, from which the blades are carried. The shaft f is steppedat the bottom of the tank and projects through the cover 6, theprojecting end being proa full, clear, and exact descripinvention, suchas will enable- Patented June 12, 1906.

I vided with a bevel gear-wheel g, arranged to engage a correspondingbevel gear-wheel '9, fixed to-a power-shaft g, as shown, which is to berotated by any suitable means when it is desired to operate the stirrer.

The space 11 between the tank a and its casing a may be supplied with acooling liquid, such as water, through the water-inlet pipe h, providedwith a valve h for controlling the fiow of water to the space i. Abranch pipe Zr, leading from the pipe h to the interior of the tank a,serves to supply water -to the latte-rfor a purpose hereinafter eX-plained. The pipe 7c is controlled by a valve 7c, and in the pipe itbeyond the valve is is provided another valve 71, whereby the water toboth the space i and the interior of the tank a may be controlledsimultaneously. In order to remove the water from the tank a, awater-outlet valve Z is arranged at the bottom of the tank. -Near thebottom and within the tank a is arranged a spiral coil n, provided witha pluralit of holes, whereby steam may be admitte to the tank, the saidcoil '12, being supplied with steam through a pipe m, controlled by acock m from a steam: pipe p, which also admits steam to the space Lthrough a cook 77, an additional cock p being provided in the pipe 79outside its connection with the pipe m. The space '0 may be emptied byan outlet-cock 0. The contents of the tank a may be emptied through alarge outlet-valve g at its bottom.

In carrying out my improved process with the above apparatus Ipreferably proceed as follows: The marine-animal oil to be acted upon issupplied to the tank through the manhole, whose plate 0 is then secured1n place. Then twenty to twenty-five per cent. of sulfuric acid of 1.84specific gravity is added to the marine-animal oil through the pipe 61and sprayer d, the oil being stirred continuously by the stirring-bladese. Finely-ground n1- trites are then added through the manhole m such aquantity that the amount of .free n1- trous acid will be substantiallyfive per cent. of the oil which is being treated. In order to regulatethe temperature of the oil according to its quality, cold water may besupplied to the space 2' through the pipe h, 1t being preferable withthis process tomalntam the temperature somewhat below centigrade, andpreferably not exceeding 40 to 50 centigrade. The stirring is continueduntil the reaction has terminated, which requires usually several hours.Thereafter the stir- IIO ring-blades e are stopped, and water of suit- Iable temperature is supplied to the tank a any surplus sulfuricand'nitrous acids, the wash-water being let off through the valve 1.

In order to remove any sulfo fatty acids which may still remain in thetallow, steam is supplied to the tank through the coil n,

whereupon the tallow may be again washed, 1 o if necessary,l' ysupplying more water through the pipe lc and drawing it from the tankthrough the outlet Z. 'In order to free the solid tallow, which is nowodorless, from any remaining water, the space i may be emptied of itswater by opening the valve 0, and steam may be admitted to said spacethrough the steam-pipe p, the heat of the steam rapidly evaporating thesaid remaining water. As soon as this is done the tallow may be runthrough the tank by opening the outlet-valve g. The effect of thesulfuric acid on this process consists, on the one hand, in convertingthe lycerids of the marine-animal oil into glycerin and free fatty acidsand, on the other 2 5 hand, in changing the oleic acid intosulfo-oxystearic acid, which latter on being further treated with steamis converted into sulfuric acid and oxystearic acid. The nitrous acidproduced by the effect of the sulfuric acid on the nitrites changes theoleic acid into solid elaidic acid, (0 11 0 at the same time completelydecomposing, through the eflect of the acids, the strong-smellingpartsof the marineanimal oil, which consists chiefly of tertiary amins.

By the common and-simultaneous treatment of the marine-animal oil withsulfuric and nitrous acid not only the. maximum quantity of liquid fattyacids contained therein is converted into solid fatty acids, but alsothe stron repulsive smell is completely removed, w ile anhydroussubstances are also formed which present a characteristicgfeature of thenew product. These anhydrous substances or anhydrids are byproductsformed by the action of sulfuric acid upon the oleic acid of themarine-animal oils and consist principally of anhydrid of oxystearicacid and anhydrid of oleic acid.

If it is desired to treat marine-animal oils with sulfuric acid only,similar results may be obtained by omitting the step consisting in theaddition of the ground nitrites described above and maintaining thetemperature 55 above 50 centigrade and preferably slightly above 60cent-igrade, sulfuric acid 0 66 Baum being added in a quantity such asto be at least twenty-five per cent. of the oil which is being treated.The product resulting from this treatment with sulfuric acid only isalso without smell, although the production of' solid acids is less thanon simultaneously treating with the two acids at the lower temperature.

The transformation of the strong-smelling amins of the marine-animaloils into odori less salts by means of sulfuric acid and nithrough thepipe is simply in order to remove l trous acid is to be seen by thefollowing reactions:

1. Sulfuric acid: 7

(1) Methylamin.

2(NH,CH )-r-H,SO =(NH CHQ ILSO,

Methylamin sulfate. (2) Dimethvlamiu.

s)z+ 2 4=( a)2)9 2 4 Dimethylamin sul- 7 S fate. (3) Trimeihylamin.

s)s)Ti- Q 4=( )Q :I)3M 2 4 Trimethylamin sulfate.

II. Nitrous acid:

(1) Trimethyiamin.

N(CH +HNO =N (CH HNO Trimetliylamin nitrate.

The odorlesssalts thus obtained being dissolved in water are removed bywashing.

The treatment of marine-animal oils with two as well as with one acidunder the conditions stated above can of course be carried out on allkinds of such oils, consequently on such as are obtained from fish,seal, and whales. The product thus obtained, which may be calledmarine-animal-oil tallow, has the appearance of ordinary tallow and iswithout smell. However, the ingredients of such tallowfdifier from thoseof the ordinary tallow in the fact that the former does not 5 consist ofglycerids of the free fatty acids, but of free fatty acidsthemselves-that is to say, to the extent ofsixty to seventy per cent. ofsolid, twenty to thirty per cent. of liquid fatty acids, and ten percent. of anhydrous substances, which latter substances enable the newproductto be used as a greasing or lubricating material.

In the manufacture of hard soap and candles the new product completelyreplaces the ordinary tallow and has the further advantage of notbecoming rancid. By reason of the properties of the new product-via, its

consistency, increased standard of solid fatty acids, and absence ofsmellit is adapted for use in many industries.

What I claim, and desire to protect by Letters Patent is 1. The processof purifying marine-animal oils which consists in converting thestrongsmelling amins into soluble salts and remov-' ing the salts.

2. The process of purifying 1n arine-anim a1 oils which consists insubjecting the oils to the action of nitrous acid and a mineral acid,and washing the product.

3. The process of treating marine-animal oil, which consists inconverting the strongsmelling amins of such an oil into odorless saltsand then removing said odorless salts.

4. The process of treating marine-animal oils, which consists in actingupon such an oil with sulfuric and nitrous acids to convert the stron-smelling amins into odorless salts, and t en removing said odorlesssalts.

5. The process of treating marine-animal oils, which consists in actingupon such an oil 7 with sulfuric and nitrous acids and afterwardtreating the resultant productwith steam.

t oils, which consists in acting upon such an oil with sulfuric andnitrous acids at a temperature not above60 centigrade, and afterwardtreating the resultant product with steam.

'7. The process of treating marine-animal oils, which consists in actingupon such an oil with sulfuric and nitrous acids, afterward treating theresultant product with steam and then washing said product.

8. The process of treating marine-animal oils, which consists in actingupon such an oil with sulfuric and nitrous acids, then washing theresultant product, then submitting it to the action of steam, againwashing it, and finally evaporating off any moisture remaining. a

9. The process of treating marine-animal oils, which consists in addingsulfuric acid and nitrites to such an oil, stirring the mixture, washingit and then treating it with steam. I

10. The process oftreating marine-animal oils, which consists'iii addingsulfuric acid and nitrites to such an oil, maintaining the mixture at atemperature above centigrade while stirring it and afterward acting uponthemixture with steam.

11. The process of treating marine-animal oils, which consists in addingsulfuric acid and nitrites to such an oil, maintaining the mixture at atemperature above 50 centigrade and stirring it, then washing it, and

, then submitting it to the action of steam. 6. The process of treatingmarine-animal 12. The process of treating marine-animal oils,'whichconsists in adding sulfuric acid and nitrites to such an oil,maintaining the mixture at a temperature above 50 centigrade, stirringit for several hours, then washing it, then submitting it to the actionof steam, again washing it and finally evaporating off any moistureremaining.

13. The process of treatin marine-animal oils, which consists in ad ingtwenty to twenty-five per cent. of sulfuric acid to such an oil, addingground nitrites in sufficient quantit to produce substantially five percent. 0 free nitrous acid, maintaining the temperature below 60centigrade, stirring the .mixture,v then washing the resultant product,then submitting it to the action of steam and finally again washing it.

' 14. The new product, marine-animal-oil tallow, consisting of sixty toseventy per cent. of solid fatty acids, twenty to thirty per cent. ofliquid fatty acids and ten per cent. of anhydrous substances.

In testimony whereof I affix my signature 1 presence of two witnesses.

MICHAEL POTOLOWSKY.

